Herbicidal alpha heterocyclic carbinol carbamates, ureas and N-alpha-substituted acetylcarbamates

ABSTRACT

Novel heterocyclic carbinol carbamates, ureas and N-acetyl-carbamates are provided which exhibit primarily preemergence control of broadleaf weeds with good selectivity for corn and certain other crops.

FIELD OF THE INVENTION

This invention relates in general to novel heterocyclic carbinol carbamates, ureas and N-substituted acetylcarbamates and their derivatives. The invention also relates to processes for the synthesis of the aforementioned compounds and the use of said compounds. In one aspect, this invention is directed to novel heterocyclic carbinol carbamates, ureas and N-substituted acetylcarbamates which exhibit primarily preemergence control of broadleaf weeds. In general, the compounds exhibited good selectivity towards corn and other crops.

BACKGROUND OF THE INVENTION

Prior to the present invention, several aromatic carbamate derivatives of benzoxazol-2-yl oxy compounds were known to exhibit herbicidal activity. However, there does not appear to be any common link in this knowledge from which one could predict herbicidal activity in other benzoxazoles, or for that matter, tetrahydrobenzoxazole, benzofuran or imidazole type structures. Additionally the ideal combination of properties relating to effective broad spectrum weed control with appropriate crop selectivity is still a much sought after goal.

Accordingly, it is an object of the present invention to provide novel heterocyclic alpha-substituted carbinol compounds and processes for their preparation which exhibit preemergence control of broadleaf weeds and may be applied safely to important crops. Specifically the compounds are novel heterocyclic alpha-substituted carbinol carbamates, ureas and N-alpha-substituted acetylcarbamates.

A further object of this invention is to provide herbicidal compositions comprised of a carrier and the novel compounds described herein as the active ingredient.

A still further object of the invention is to provide a process for controlling broadleaf weeds by applying to such weeds herbicidal compositions containing the novel compounds.

These and other objects will readily become apparent to these skilled in the art.

SUMMARY OF THE INVENTION

In its broad aspect, the invention relates to novel alpha heterocyclic carbinol carbamates, ureas and N-alpha-substituted acetylcarbamates; herbicidal compositions containing same; and processes for their preparation and use. The novel compounds of this invention can be represented by the following generic formula: ##STR1## wherein the various substituents are identified below.

DETAILED DESCRIPTION OF THE INVENTION

As previously indicated, this invention is directed to the synthesis of novel alpha heterocyclic carbinol carbamates, ureas and N-alpha-substituted acetylcarbamates which exhibit excellent pre-emergence control of broadleaf weeds and a high degree of selectivity for corn and certain other crops.

The compounds of this invention are defined by the generic formula: ##STR2## wherein A is ##STR3## X is O, S or NR; Y is O, S or NR;

Z is O, S or NR;

R is H or alkyl;

R¹ through R⁹ inclusive and R¹³ through R¹⁶ inclusive are individually: hydrogen, halogen, alkyl, cycloalkyl, haloalkyl, halocycloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, nitro, cyano; or phenyl, phenoxy, or phenylthio unsubstituted or substituted with alkyl, alkoxy, alkylthio, halogen, nitro, cyano, amino, haloalkyl, alkylamino, dialkylamino, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkanoyl, aroyl, alkenyl, or alkynyl;

R¹⁰ is hydrogen, alkyl, cycloalkyl, haloalkyl, halocycloalkyl, aryl, cyano, alkynyl; and

R¹¹ and R¹² are individually hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio; or phenoxy, phenylthio, or aryl; unsubstituted or substituted with halo, alkyl, alkoxy, nitro, cyano, alkylthio, alkylamino; alpha-haloacetyl, acetyl, alpha-alkylthioacetyl, alpha-aminoacetyl, alpha-alkoxyacetyl, alpha-phosphonoacetyl, phosphinoacetyl, phosphinylacetyl, phosphoacetyl, propionyl.

The preferred compounds of this invention are those

in which

A is ##STR4## R¹ through R⁴ inclusive are hydrogen; and X, Y and Z are O.

The more preferred compounds of this invention are the preferred compounds

wherein

R⁷ is hydrogen; and

R⁵, R⁶, R⁸ and R⁹ are individually hydrogen, C₁ -C₃ alkyl, or halogen.

The most preferred compounds of the invention are the more preferred compounds wherein

R¹¹ and R¹² are individually hydrogen, C₁ -C₃ alkyl, unsubstituted acetyl or halosubstituted acetyl.

It is accordingly, readily apparent from the scope of the preceding formulae that this invention encompasses a wide variety of novel heterocyclic carbinol carbamates, ureas and N-alpha-substituted acetylcarbamates. Tables A-C which follow, set forth certain subclasses within the broad generic formula and illustrate specific compounds falling within the particular classes. These examples will serve to illustrate but not limit the areas defined by this invention.

    TABLE A       ##STR5##        X Y Z R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8      R.sup.9 R.sup.10 R.sup.11 R.sup.12        O O O H H H H F H H H H H CH.sub.3 H O O O H H H H Br H H H H H      CH.sub.3 H O O O H H H H F H H H F H CH.sub.3 H O O O H H H H Cl H H H F      H CH.sub.3 H O O O H H H H CH.sub.3 H H H CH.sub.3 H CH.sub.3 H O O O H      H H H CH.sub.3 H H H H H CH.sub.3 H O O O H H H H CH.sub.3 H H CH.sub.3      H H CH.sub.3 H O O O H H H H H OCH.sub.3 H H H H CH.sub.3 H O O O H H H      H Cl H H H F H CH.sub.3 CH.sub.3 O O O H H H H H H H H H H CH.sub.3      CH.sub.3 O O O H H H H Cl H H H H H CH.sub.3 CH.sub.3 O O O H H H H      CH.sub.3 H H H H H CH.sub.3 CH.sub.3 O O O H H H H H CH.sub.3 H H H H Et      H O O O H H H H H H H H H H Et H O O O H H H H CH.sub.3 H H H H H Et H O      O O H H H H Cl H H H F H Et H O O O H H H H Cl H H H H H Et H O O O H H      H H Et H H H H H CH.sub.3 H O O O H H H H CF.sub.3 H H H H H CH.sub.3 H      O O O H H H H H H F H H H CH.sub.3 H O O O H H H H H H Cl H H H CH.sub.3      H O O O H H H H CH.sub.3 H CH.sub.3 H H H CH.sub.3 H O O O H H H H H      CH.sub.3 H H H H CH.sub.3 H O O O H H H H H F H H H H CH.sub.3 H O O O H      H H H H CF.sub.3 H H H H CH.sub.3 H O O O H Cl H H F H H H H H CH.sub.3      H O O O H Cl H H CH.sub.3 H H H H H CH.sub.3 H O O O H Cl H H Cl H H H F      H CH.sub.3 H O O O H Cl H H Cl H H H H H CH.sub.3 H O O O H CH.sub.3 H H      CH.sub.3 H H H H H CH.sub.3 H O O O H CH.sub.3 H H Cl H H H H H CH.sub.3      H O O O H CH.sub.3 H H Cl H H H F H CH.sub.3 H O O O H H CH.sub.3 H Cl H      H H F H CH.sub.3 H O O O H H CH.sub.3 H CH.sub.3 H H H H H CH.sub.3 H S      O O H H H H Cl H H H H H CH.sub.3 H O S O H Cl Cl H CF.sub.3 H H H H H      CH.sub.3 CH.sub.3 S O O H H H H Cl H H H H H CH.sub.3 H O O O H H H H H      H H H H H CH.sub.3 H O S O H Cl Cl H CF.sub.3 H H H H H CH.sub.3      CH.sub.3  N(CH.sub.3) S S H SO.sub.2       CH.sub.3 H H H H H      ##STR6##       H CH.sub.3 H H       S O S H NO.sub.2 H H H H N(CH.sub.3).sub.2 H H      ##STR7##       H OCH.sub.3  O S O H H H H Cl H H H H H CH.sub.3 H  S O S H Cl H      CF.sub.3 OCH.sub.3 H H H H CN       ##STR8##       H  O S S H OCH.sub.3 H H H CH.sub.2 SCH.sub.3 H H H CCCH.sub.3 n-butyl      H O S O H H H H Cl H H H F H CH.sub.3 H S O O H NO.sub.2 Cl H NO.sub.2 H      NO.sub.2 H H CH.sub.3 CH.sub.3 CH.sub.3 O O O Cl Cl Cl Cl H SO.sub.2      CH.sub.3 H H H CF.sub.3 H H N(CH.sub.3) O S CF.sub.3 H CF.sub.3 H H H      CH.sub.2 N(CH.sub.3).sub.2 H H CH.sub.3 CH.sub.3 CH.sub.3 O O O H Br H H      Cl H CF.sub.3 H H H CH.sub.3 H       O O S H NO.sub.2 H NO.sub.2 H      ##STR9##       H H H H CH.sub.3 H       NH O O H      ##STR10##       H H H CCH H H H H CH.sub.3 CH.sub.3  O O O H H H H Cl H OCF.sub.3 H H H      CH.sub.3 H S NH O H H H H H H H H H H CH.sub.3 H  O NH S H Cl H Cl Cl H      H H Cl H       ##STR11##       H  O NH O H H H H Cl H H H H H CH.sub.3 CH.sub.3 O O O CH.sub.3 H H H      Cl H H H F H CH.sub.3 H O O O CH.sub.3 H H H F H H H F H CH.sub.3 H O O      O Cl H H H Cl H H H F H CH.sub.3 H O O O F H H H F H H H F H CH.sub.3 H      O O O H H H CH.sub.3 Cl H H H F H CH.sub.3 H O O O H H H F F H H H F H      CH.sub.3 H O O O H H H CH.sub.3 CH.sub.3 H H H H H CH.sub.3 H  O O O H H      H H       ##STR12##       H H H H H CH.sub.3 H

                                      TABLE B                                      __________________________________________________________________________      ##STR13##                                                                     X Y Z R.sup.1                                                                           R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                           R.sup.5                                                                           R.sup.6                                                                          R.sup.7                                                                          R.sup.8                                                                           R.sup.9                                                                          R.sup.10                                                                          R.sup.11                                                                          R.sup.17                                     __________________________________________________________________________     O O O H  H H H  Cl H H H  H H  CH.sub.3                                                                          Cl                                           O O O H  H H H  Cl H H F  H H  CH.sub.3                                                                          Cl                                           O O O H  H H H  CH.sub.3                                                                          H H H  H H  CH.sub.3                                                                          Cl                                           O O O H  H H H  H  H H H  H H  CH.sub.3                                                                          Cl                                           O O O CH.sub.3                                                                          H H H  F  H H H  F H  CH.sub.3                                                                          Cl                                           O O O F  H H H  Cl H H H  F H  H  Cl                                           O O O Cl H H H  CH.sub.3                                                                          H H H  H H  CH.sub.3                                                                          Cl                                           O O O H  H H H  F  H H H  F H  CH.sub.3                                                                          Cl                                           O O O H  H H H  F  H H H  F H  CH.sub.3                                                                          SCH.sub.3                                    O O O H  H H H  F  H H H  Cl                                                                               H  H  SEt                                          O O O H  H H H  F  H H H  Cl                                                                               H  CH.sub.3                                                                           ##STR14##                                   O S O H  H H H  F  H H H  Cl                                                                               H  H  Cl                                           __________________________________________________________________________

                                      TABLE C                                      __________________________________________________________________________      ##STR15##                                                                     X Y Z R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                          R.sup.6                                                                          R.sup.7                                                                          R.sup.8                                                                          R.sup.9                                                                          R.sup.10                                                                          R.sup.11                                                                          R.sup.12                                                                          R.sup.13                                                                          R.sup.14                                                                          R.sup.15                                                                          R.sup.16                           __________________________________________________________________________     O O O H  H  H H Cl                                                                               H H H F H  CH.sub. 3                                                                         H  H  H  H  H                                  O O O CH.sub.3                                                                          H  H H Cl                                                                               H H H F H  CH.sub.3                                                                          H  H  H  H  H                                  O O O CH.sub.3                                                                          H  H H F H H H F H  CH.sub.3                                                                          H  H  H  H  CH.sub.3                           O O O CH.sub.3                                                                          CH.sub.3                                                                          H H Cl                                                                               H H H F H  CH.sub.3                                                                          H  H  H  H  H                                  O O O F  H  H H F H H H F H  CH.sub.3                                                                          H  H  H  H  H                                  __________________________________________________________________________

The novel compositions of this invention can be prepared in two steps. Step I: preparation of appropriate alcohols, thiols, and amines, Step II: carbamoylation.

Preparation of appropriate alcohols and/or thiols can be achieved according to a variety of methods as illustrated by the following reaction schemes. ##STR16## wherein: X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ are as described previously. ##STR17## Wherein: X' are OCH₃, OCH₂ CH₃, ##STR18## Y' are Li.sup.⊕, Na.sup.⊕, MgBr.sup.⊕ X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ are as described previously. ##STR19## Wherein: B' is O, S,

X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ are as described previously. ##STR20## Wherein: B' is O, S.

X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ are as described previously. ##STR21## Wherein: X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ are as described previously.

The substituted 2(benzoxazole)methanols illustrated in Method I can be effected by metallation of 1,3-benzoxazoles with one equivalent of n-butyllithium at -78° C., followed by the addition of appropriate aldehydes or ketones. This reaction may be performed in anhydrous diethyl ether or tetrahydrofuran. (Beraud and J. Metzger, Bull. Soc. Chim. France, 2072-4 (1962); H. Gilman and J. A. Beel, J. Am. Chem. Soc. 71, 2328-31 (1949).

Preparation of appropriate heterocycles can be achieved by the following reaction schemes. ##STR22## (Societe de Produits Chemiques et de Synthese. Fr. 1493401, Sept. 1, 1967; also CA 1968, Vol 69. 2856 g.) ##STR23## (Hellmut Bredereck and Rudolf Gompper, Chem. Ber. 87, 700-7 (1954))

The preparation of ketones in Method II can be achieved by metallation of 1,3-benzoxazoles as described in Method I, followed by addition of appropriate methyl benzoates (or ethyl benzoates, benzoyl chlorides, benzoyl imidazoles, phenyl nitriles). The desired carbinols can then be effected by nucleophilic addition of appropriate organometallic compounds (such as alkylithium, phenyllithium, Grignard reagents) or nitrile ion to the ketones.

The condensation reaction outlined in Method III can be accomplished using essentially equimolar ratios of the appropriate α-hydroxy acids (or α-thio-acids*) and o-aminophenols (or o-aminothiophenols, o-aminoanilines) in a variety of conditions. (*It can be prepared by the reaction of the appropriate α-bromophenylacetic acid with sodium sulfide nonahydrate (P. A. Levene; T. Mori; L. A. Mikeska, J. Biochem (Tokyo) 75, 337-365, 1927), followed by reduction of the disulfide with zinc in acetic acid. See: N. Wardell in "Chemistry of the Thiol Group", Patai, S., Ed.; Wiley; New York, 1974; Part 1, pp. 220-229).) This may be effected by azeotropically removing water via an inert, high-boiling organic solvent such as xylene. (F. Gualtiere, G. Brody, A. H. Fieldsteel and W. A. Skinner, J. Med. Chem. 14, 546-9 (1971).) It can also be achieved by refluxing the two components in an aqueous hydrochloric acid solution (Brit. 885,520 (1961), J. R. Geigy A-G.) or heating the two reagents in a sealed tube at an elevated temperature. (V. M. Zubarovskii; Zhur, Obshchei Khim. 21, 2199- 205 (1951).)

The reaction illustrated in Method IV can be conducted using equimolar ratios of the appropriate α-hydroxy nitriles (or α-thio nitriles) and o-aminophenols (or o-aminothiophenols, o-aminoanilines) in refluxing methanol. (A. Banashek and M. H. Shchukina; Zh. Obshch. Khim. 32, 205-8 (1962).)

The reaction outlined under Method V can be accomplished by halogen-lithium exchange of 2-bromo-1,3-benzoxazoles with one equivalent of n-butyllithium at -78° C. The corresponding lithium salt can then react with a variety of aldehydes or ketones to form the desired alcohols. This reaction may be performed in anhydrous diethyl ether or tetrahydrofuran.

In general, the alcohols prepared in Method I to V are well-known compounds.

Preparation of appropriate amines can be achieved by the following reaction schemes. ##STR24## Wherein: X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, are as described previously. ##STR25## Wherein: X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ are as described previously.

The reaction scheme outlined in Method VI demonstrates the preparation of amines. They can be achieved by formation of appropriate oximes, followed by reduction with powdered zinc in aqueous ammonia (V. V. Avidon and M. N. Shchukina; Khim. Geterotsikl. Soedin., Akad. Nauk Latv. SSR, 64-8 (1965); T. P. Sycheva, I. D. Kiseleva and M. N. Shchukina; Khim. Geterotsikl. Soedin., 690-3 (1966).)

The reaction scheme illustrated in Method VII can be effected by protecting the α-amino nitriles with a benzoyloxycarbonyl group. The nitriles are treated with dry hydrogen chloride in a mixture of absolute ethanol and absolute diethyl ether to yield the corresponding iminoether hydrochlorides. (A. J. Hill and I. Rabinowitz, J. Am. Chem. Soc. 48, 732-7 (1926); M. Mengelberg, Chem. Ber., 89, 1185-95 (1956).)

Free iminoethers can be obtained by treatment of the iminoeher hydrochloride with an aqueous concentrated potassium carbonate solution. (Y. Hirotsu, T. Shiba, and T. Kaneko; Bull. of Chem. Soc. of Japan, 40, 2945-49 (1967).) Coupling of the imino ether with appropriate o-aminophenols, o-aminothiophenols or o-aminoanilines gives a protected amine (2) which can then be treated with 30% hydrogen bromide in acetic acid to afford the hydrobromide of the desired amine (3). (Y. Hirotsu, T. Shiba, and T. Kaneko; Bull. of Chem. Soc. of Japan, 43, 1564-67 (1970).) The amine (3) can be obtained by treatment with aqueous ammonia.

The carbamoylation illustrated in Method VIII can be achieved by reacting the appropriate alcohols, thiols, or amines and one equivalent of alkyl isocyanate (or aryl isocyanate, alkyl isothiocyanate, aryl isothiocyanate) in ethyl acetate or methylene chloride at room temperature. Catalytic amounts of dibutyltin diacetate can enhance the reaction rate. ##STR26## Wherein: X, Y, Z, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁ are as described previously. ##STR27## Wherein: X, Y, Z, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂ are as described previously. ##STR28## Wherein: X, Y, Z, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂ are as described previously.

The reaction outlined in Method IX can be effected by using equimolar ratios of the alcohols (or thiols, amines) and appropriate carbamoyl chloride in the presence of an acid acceptor. Suitable acid acceptors are tertiary amine bases such as triethylamine, pyridine or N,N-dimethyl-4-aminopyridine. This reaction may be performed in a variety of refluxing solvents, such as acetonitrile, methyl chloride, ethylacetate.

The preparation of carbamates or ureas in Method X can be achieved by reaction of appropriate alcohols, thiols or amines with phosgene (or thiophosgene), followed by the addition of appropriate primary amines (or secondary amines) in the presence of an acid acceptor. Suitable acid acceptors are tertiary amine bases such as triethylamine or pyridine.

The synthesis of N-(α-haloacyl) carbamates or ureas in Method XI can be achieved by reacting the appropriate alcohols, thiols or amines with N-alpha-haloacyl-N-hydrocarbyl carbamoyl halides in the presence of 1.0 equivalent of an acid acceptor. Suitable acid acceptors are tertiary amine bases such as triethylamine, pyridine, or N,N-dimethyl-4-aminopyridine. ##STR29## Wherein X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are as described previously and R¹⁷ is as described for R¹³. ##STR30## Wherein X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are as described previously and R¹⁷ is as described for R¹³.

The reaction outlined in Method XII can be effected by using equimolar ratios of the appropriate carbamates (or ureas) and appropriate α-haloacylhalides in the presence of an acid acceptor. Suitable acid acceptors are tertiary amines bases such as triethylamine, pyridine or N,N-dimethyl-4-aminopyridine. The solvent used for this transformation may be methylene chloride, acetonitrile or ethyl acetate.

The following examples illustrate the best mode presently contemplated for the practice of this invention.

EXAMPLE I 2-(o-chloro-α-hydroxybenzyl)benzothiazole

47 mL of 1.6M-butyllithium in hexane was added dropwise to a solution of benzothiazole (10 g, from Aldrich) and diethyl ether (200 mL) at -78° C. under nitrogen. The red brown solution was stirred at -78° C. for 30 min., followed by the addition of a solution of o-chlorobenzaldehyde (10.8 g) and diethyl ether (100 mL) at -78° C. The mixture was then stirred at -78° C. for 2 hours before it was allowed to warm to room temperature and stirred at room temperature overnight.

It was then quenched by the addition of 7.5% NH₄ Cl aqueous solution (200 mL) and extracted with three portions of diethyl ether. The combined ether extracts were washed with brine, dried over Na₂ SO₄, filtrate and concentrated in vacuo to yield a yellow solid. Recrystallization from hexane and ethyl acetate afforded 9.9 g of yellow needle crystals, mp 118°-120° C.

Anal. C₁₄ H₁₀ ClNOS: Calc. C, 60.97; H, 3.66; N, 5.08. Found C, 61.05; H, 3.55; N, 5.09.

EXAMPLE II 2(α-hydroxybenzyl)benzothiazole

A mixture of o-aminothiophenol (23.5 g) and dl-mandelic acid (25 g) was refluxed in xylene with a Dean-Stark tube for two days.

After cooling, the solution was washed with 1N HCl aqueous solution (500 mL), 5% Na₂ CO₃ aqueous solution (500 mL) and brine. It was dried over MgSO₄, filtered and concentrated in vacuo to yield a solid residue. Recrystallization from toluene afforded 16.6 g of white crystals.

Anal. C₁₄ H₁₁ NOS: Calc. C, 69.68; H, 4.60; N, 5.81. Found C, 70.10; H, 4.63; N, 5.78.

EXAMPLE III 2(α-aminobenzyl)benzothiazole

Ethyl benzoate (60.1 g, 0.4 mol.) in 200 mL of diethyl ether was added dropwise to 0.4 mol. of benzothiazolyllithium in 700 mL of diethyl ether (see Example I) at -78° C. and the mixture was then stirred 2 hours at -78° C. and overnight at room temperature. It was quenched by the addition of aqueous 10% NH₄ Cl solution and extracted with three portions of diethyl ether. The combined ether extracts were washed with brine, dried over Na₂ SO₄, filtered, concentrated in vacuo and recrystallized from hexane and ethyl acetate to afford 41.5 g of light-brown crystals (phenyl 2-benzothiazolyl ketone).

A mixture of phenyl 2-benzothiazolyl ketone (35 g), hydroxylamine hydrochloride (10.5 g), pyridine (175 mL) and ethanol (175 mL) was refluxed for 4 hours. After cooling, the solution was concentrated in vacuo. The solid residue was washed with water, dried in vacuo, and 36.6 g of oxime was obtained.

The mixture of oxime (21.6 g), aqueous ammonia (800 mL) and ethanol (80 mL) was stirred with 16.7 g of powdered zinc at 50°-60° C. for 30 minutes, and another 2.5 g of powdered zinc was then added. The suspension was stirred at 50°-60° C. for 4 hours.

After cooling, the gray suspension mixture was extracted with three portions of methylene chloride. The combined methylene chloride extracts were dried over Na₂ SO₄, filtered and concentrated in vacuo. Immediately after the addition of 1N HCl (200 mL) to the residue, a yellowish white solid was formed. It was filtered washed with water, then methylene chloride. 19.5 g of 2-(α-aminobenzyl)benzothiazole hydrochloride as a white solid was obtained.

The hydrochloride was stirred with aqueous ammonia and methylene chloride, and the aqueous layer was extracted with two portions of methylene chloride. The combined methylene chloride extracts were washed with brine, dried over Na₂ SO₄, filtered and concentrated in vacuo. 13.1 g of white solid, as desired product, was obtained, mp. 68°-70° C.

Anal. C₁₄ ₁₂ N₂ S: Calc. C, 69.96; H, 5.03; N, 11.66. Found C, 69.88; H, 5.18N, 11.55.

EXAMPLE IV N-methylcarbamoyloxy-2-(o-chloro-α-hydroxybenzyl)benzoxazole

A mixture of 2-(o-chloro-α-hydroxybenzyl)benzoxazole (3 g), methyl isocyanate (1.06 mL), a catalytic amount of dibutyltin diacetate and methylene chloride (50 mL) was stirred at room temperature in a pressure bottle overnight, after which the mixture was concentrated in vacuo. The solid residue was partititioned between ethyl acetate-diethyl ether and water. The organic extract was dried over Na₂ SO₄, filtered and concentrated in vacuo to yield the corresponding carbamate. Recrystallization from toluene afforded 2.2 g of crystals, mp. 116°-117° C.

Anal. C₁₆ H₁₃ ClN₂ O₃ : Calc. C, 60.67; H, 4.14; N, 8.85. Found C, 61.14; H, 4.17; N, 8.66.

EXAMPLE V Preparation of α-(2-benzoxazolyl)-2-chlorophenyl-N-chloroacetyl-N-methylcarbamate

To a mixture of 2-(0-chloro-α-hydroxybenzyl)benzoxazole (5.0 g, 0.019 mol) and N-chloroacetyl-N-methylcarbamyl chloride (3.23 g, 0.019 mol, 1.1 eq) in acetonitrile (150 mL) under a nitrogen atmosphere at 0° C. was added triethylamine (2.6 mL, 0.019 mol. 1 eq) in acetonitrile (75 mL). The resulting mixture was stirred at room temperature for 3 hours. The mixture was evaporated in vacuo. The residue was partitioned between CH₂ Cl₂ and water. The organic layer was dried over anhydrous Na₂ SO₄ and evaporated. The residue was purified by chromatography on silica gel using 100% CH₂ Cl₂ to give 1.7 g (23%) of desired product as an oil.

Anal. C₁₈ H₁₄ Cl₂ N₂ O₄ : Calc. C, 54.98; H, 3.59. Found C, 54.71; H, 3.78.

EXAMPLES 1-46

In a manner similar to that employed in the preceding examples, and using one of the synthesis schemes previously disclosed, other compounds of this invention were prepared. The identity of the substituents on the generic formulae and the analytical data are set forth in Tables I-IV below:

                                      TABLE I                                      __________________________________________________________________________     HERBICIDAL STRUCTURES                                                           ##STR31##                                                                     Example                                                                             R.sup.1                                                                          R.sup.2                                                                           R.sup.3                                                                           R.sup.4                                                                          R.sup.5                                                                             R.sup.6                                                                            R.sup.7                                                                           R.sup.8                                                                           R.sup.9                                                                           R.sup.10                                                                          R.sup.11                                                                          R.sup.12                                                                              X   Y  Z                         __________________________________________________________________________      1   H H  H  H Cl   H   H  H  F  H  H  CH.sub.3                                                                              O   O  O                          2   H H  H  H F    H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                          3   H H  H  H Br   H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                          4   H H  H  H Cl   H   H  H  F  H  H  CH.sub.3 (CH.sub.2).sub.3                                                             O   O  O                          5   H H  H  H CH.sub.3                                                                            H   H  CH.sub.3                                                                          H  H  H  CH.sub.3                                                                              O   O  O                          6   H H  H  H H    F   H  H  H  H  H  CH.sub.3                                                                              O   O  O                          7   H H  H  H H    CH.sub.3                                                                           H  H  H  H  H  CH.sub.3                                                                              O   O  O                          8   H H  H  H H    OCH.sub.3                                                                          H  H  H  H  H  CH.sub.3                                                                              O   O  O                          9   H H  H  H CH.sub.3                                                                            H   CH.sub.3                                                                          H  H  H  H  CH.sub.3                                                                              O   O  O                         10   H H  H  H Cl   H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         11   H H  H  H Cl   H   H  H  H  H  CH.sub.3                                                                          CH.sub.3                                                                              O   O  O                         12   H H  H  H CF.sub.3                                                                            H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         13   H H  H  H CH.sub.3                                                                            H   H  H  H  H  CH.sub.3                                                                          CH.sub.3                                                                              O   O  O                         14   H H  H  H Cl   H   H  H  H  H  H  CH.sub.3 CH.sub.2                                                                     O   O  O                         15   H H  H  H H    CF.sub.3                                                                           H  H  H  H  H  CH.sub.3                                                                              O   O  O                         16   H H  H  H Cl   H   H  H  F  H  H  CH.sub.3 CH.sub.2                                                                     O   O  O                         17   H H  H  H CH.sub.3                                                                            H   H  H  H  H  H  CH.sub.3 CH.sub.2                                                                     O   O  O                         18   H H  H  H H    H   H  H  H  H  H  CH.sub.3 CH.sub.2                                                                     O   O  O                         19   H H  H  H H    H   H  H  H  H  CH.sub.3                                                                          CH.sub.3                                                                              O   O  O                         20   H H  H  H Cl   H   H  H  F  H  CH.sub.3                                                                          CH.sub.3                                                                              O   O  O                         21   H H  H  H H    CH.sub.3                                                                           H  H  H  H  H  CH.sub.3 CH.sub.2                                                                     O   O  O                         22   H H  H  H F    H   H  H  F  H  H  CH.sub.3                                                                              O   O  O                         23   H H  H  H CH.sub.3                                                                            H   H  H  CH.sub.3                                                                          H  H  CH.sub.3                                                                              O   O  O                         24   H H  H  H Cl   H   H  H  H  H  CH.sub.3                                                                          ClCH.sub.2 CO                                                                         O   O  O                         25   H H  H  H Cl   H   H  H  F  H  CH.sub.3                                                                          ClCH.sub.2 CO                                                                         O   O  O                         26   H H  H  H CH.sub.3                                                                            H   H  H  H  H  CH.sub.3                                                                          ClCH.sub.2 CO                                                                         O   O  O                         27   H H  H  H H    H   H  H  H  H  CH.sub.3                                                                          ClCH.sub.2 CO                                                                         O   O  O                         28   H H  H  H H    H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         29   H H  H  H CH.sub.3                                                                            H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         30   H H  H  H Cl   H   H  H  F  H  H                                                                                  ##STR32##                                                                            O   O  O                         31   H CH.sub.3                                                                          H  H Cl   H   H  H  F  H  H  CH.sub.3                                                                              O   O  O                         32   H CH.sub.3                                                                          H  H Cl   H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         33   H CH.sub.3                                                                          H  H CH.sub.3                                                                            H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         34   H Cl H  H Cl   H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         35   H Cl H  H Cl   H   H  H  F  H  H  CH.sub.3                                                                              O   O  O                         36   H Cl H  H CH.sub.3                                                                            H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         37   H Cl H  H F    H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         38   H H  CH.sub.3                                                                          H CH.sub.3                                                                            H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         39   H H  CH.sub.3                                                                          H Cl   H   H  H  F  H  H  CH.sub.3                                                                              O   O  O                         40   H H  H  H Cl   H   H  H  H  H  H  CH.sub.3                                                                              S   O  O                         41   H H  H  H CH.sub.2 CH.sub.3                                                                   H   H  H  H  H  H  CH.sub.3                                                                              O   O  O                         42   H H  H  H H    H   H  H  H  H  H  CH.sub.3                                                                              S   O  O                         43   H H  H  H NO.sub.2                                                                            H   H  H  H  H  H  CH.sub.3                                                                              S   O  O                         44   H H  H  H OCH.sub.3                                                                           H   H  H  H  H  H  CH.sub.3                                                                              S   O  O                         45   H H  H  H Cl   H   Cl H  H  H  H  CH.sub.3                                                                              O   O  O                         46   H H  H  H Cl   H   Cl H  H  H  H  CH.sub.3                                                                              NCH.sub.3                                                                          O  O                         47   H H  H  H Cl   H   Cl H  H  H  H  CH.sub.3 (CH.sub.2).sub.3                                                             O   O  O                         48   H H  H  H H    Cl  Cl H  H  H  H  CH.sub.3                                                                              O   O  O                         49   H H  H  H Cl   H   Cl H  H  H  CH.sub.3                                                                          CH.sub.3                                                                              O   O  O                         50   H H  H  H Cl   H   H  H  Cl H  H  CH.sub.3                                                                              O   O  O                         51   H H  H  H Cl   H   H  H  Cl H  CH.sub.3                                                                          CH.sub.3                                                                              O   O  O                         52   H H  H  H H    H   H  H  H  H  H  CH.sub.3                                                                              S   NH O                         53   H H  H  H H    H   H  H  H  H  H                                                                                  ##STR33##                                                                            S   NH O                         __________________________________________________________________________

                  TABLE II                                                         ______________________________________                                         HERBICIDAL STRUCTURES                                                           ##STR34##                                                                     Ex-                                                                            am-                                                                            pleR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8             R.sup.9           R.sup.10                                                                              R.sup.11                                                                              R.sup.12                                                                            X   Y   Z                                 ______________________________________                                         54HHHHClHHHF      H      H      CH.sub.3                                                                            O   O   O                                 ______________________________________                                    

                  TABLE III                                                        ______________________________________                                         HERBICIDAL STRUCTURES                                                           ##STR35##                                                                     Ex-                                                                            am-                                                                            ple  R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                             R.sup.5                                                                            R.sup.6                                                                            R.sup.7                                                                            R.sup.8                                                                            R.sup.9                                                                            R.sup.10 R.sup.11                                                                       XYZup.12                    ______________________________________                                         55   H     H     CH.sub.3                                                                            F   H   H   H   H   HHCH.sub.3                                                                              H O O                       56   H     H     CH.sub.3                                                                            Cl  H   H   H   F   HHCH.sub.3                                                                              H O O                       ______________________________________                                    

                                      TABLE IV                                     __________________________________________________________________________     PHYSICAL PROPERTIES OF HERBICIDAL COMPOUNDS                                                        Calculated                                                                               Found                                            Example                                                                             M.P. (°C.)                                                                    Formula  C  H  N   C   H   N                                        __________________________________________________________________________      1   134.5-136.5                                                                          C.sub.16 H.sub.22 ClFN.sub.2 O.sub.3                                                    57.4                                                                              3.6                                                                               8.4 57.49                                                                              3.39                                                                               8.34                                      2   110.0-112.0                                                                          C.sub.16 H.sub.13 FN.sub.2 O.sub.3                                   3   130.0-131.5                                                                          C.sub.16 H.sub.13 BrN.sub.2 O.sub.3                                                     53.21                                                                             3.63                                                                              7.76                                                                               53.61                                                                              3.89                                                                               7.72                                      4   97.0-98.0                                                                            C.sub.19 H.sub.18 ClFN.sub.2 O.sub.3                                                    60.56                                                                             4.81                                                                              7.43                                                                               60.55                                                                              4.86                                                                               7.46                                      5   150.5-152.0                                                                          C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                       69.66                                                                             5.85                                                                              9.03                                                                               70.00                                                                              6.03                                                                               9.02                                      6   197.5-199.0                                                                          C.sub.16 H.sub.13 FN.sub. 2 O.sub.3                                                     64.00                                                                             4.36                                                                              --  64.83                                                                              4.29                                                                               --                                        7   125.5-127.0                                                                          C.sub.17 H.sub.16 N.sub.2 O.sub.3                                                       68.91                                                                             5.44                                                                              --  68.71                                                                              5.55                                                                               --                                        8         C.sub.17 H.sub.16 N.sub.2 O.sub.4 (ir (film) 3360, 2960, 1730,                 1605, 1530, 1250, 1130 cm.sup.-1)                                     9  127.0-128.5                                                                          C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                       69.66                                                                             5.85                                                                              --  69.83                                                                              5.84                                                                               --                                       10   116-117                                                                              C.sub.16 H.sub.13 ClN.sub.2 O.sub.3                                                     60.67                                                                             4.14                                                                              8.85                                                                               61.14                                                                              4.17                                                                               8.66                                     11   123.5-127.0                                                                          C.sub.17 H.sub.15 ClN.sub.2 O.sub.3                                                     61.73                                                                             4.57                                                                              --  61.55                                                                              4.59                                                                               --                                       12    98.0-100.0                                                                          C.sub.17 H.sub.13 F.sub.3 N.sub.2 O.sub.3                                               58.29                                                                             3.74                                                                              --  57.95                                                                              3.80                                                                               --                                       13   139.5-142.5                                                                          C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                       69.66                                                                             5.85                                                                              --  69.60                                                                              5.98                                                                               --                                       14   106.5-108.5                                                                          C.sub.17 H.sub.15 ClN.sub.2 O.sub.3                                                     61.73                                                                             4.57                                                                              --  61.91                                                                              4.65                                                                               --                                       15   117.5-119.5                                                                          C.sub.17 H.sub.13 F.sub.3 N.sub.2 O.sub.3                                               58.29                                                                             3.74                                                                              --  58.62                                                                              3.92                                                                               --                                       16   118.0-119.5                                                                          C.sub.17 H.sub.14 ClFN.sub.2 O.sub.3                                                    58.55                                                                             4.05                                                                              --  58.43                                                                              4.26                                                                               --                                       17   108-110                                                                              C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                       69.66                                                                             5.85                                                                              --  69.79                                                                              5.99                                                                               --                                       18   121.0-123.0                                                                          C.sub.17 H.sub.16 N.sub.2 O.sub.3                                                       68.91                                                                             5.44                                                                              --  69.10                                                                              5.67                                                                               --                                       19   107-108                                                                              C.sub.17 H.sub.16 N.sub.2 O.sub.3                                                       68.91                                                                             5.44                                                                              --  69.07                                                                              5.50                                                                               --                                       20   --    C.sub.17 H.sub.14 ClFN.sub.2 O.sub.3                                                    58.55                                                                             4.05                                                                              --  58.12                                                                              4.15                                                                               --                                       21   --    C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                                 NMR: δ 2.32(S,3H), CH.sub.3                                              on phenyl ring                                   22   138.5-139.5                                                                          C.sub.16 H.sub.12 F.sub.2 N.sub.2 O.sub.3                                               60.38                                                                             3.80                                                                              --  60.24                                                                              3.90                                                                               --                                       23   115.5-118.0                                                                          C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                       69.66                                                                             5.85   69.40                                                                              6.11                                         24   --    C.sub.18 H.sub.14 Cl.sub.2 N.sub.2 O.sub.4                                              54.98                                                                             3.59                                                                              --  54.71                                                                              3.78                                                                               --                                       25         C.sub.18 H.sub.13 Cl.sub.2 FN.sub.2 O.sub.4                                             52.58                                                                             3.19                                                                              --  52.27                                                                              3.49                                                                               --                                       26         C.sub.19 H.sub.17 ClN.sub.2 O.sub.4                                                     61.21                                                                             4.60                                                                              --  69.85                                                                              4.60                                                                               --                                       27         C.sub.18 H.sub.15 ClN.sub.2 O.sub.4                                                     60.26                                                                             4.21                                                                              --  59.73                                                                              4.43                                                                               --                                       28   Viscous oil                                                                          C.sub.16 H.sub.14 N.sub.2 O.sub. 3                                                      68.08                                                                             5.00                                                                              9.93                                                                               69.08                                                                              4.64                                                                               9.02                                     29   114.0-115.5                                                                          C.sub.17 H.sub.16 N.sub.2 O.sub.3                                                       68.91                                                                             5.44                                                                              9.45                                                                               69.43                                                                              5.62                                                                               9.45                                     30   --    C.sub.21 H.sub.14 ClFN.sub.2 O.sub.3                                                    63.57                                                                             3.56                                                                              7.06                                                                               63.52                                                                              3.74                                                                               7.01                                     31   142.5-144.5                                                                          C.sub.17 H.sub.14 ClFN.sub.2 O.sub.3                                                    58.55                                                                             4.05                                                                              --  58.56                                                                              4.11                                                                               --                                       32   127.5-129.0                                                                          --                                                                  33   138.0-139.0                                                                          C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                       69.66                                                                             5.85                                                                              --  69.84                                                                              5.87                                                                               --                                       34   111.5-113.0                                                                          C.sub.16 H.sub.12 Cl.sub.2 N.sub.2 O.sub.3                                              54.72                                                                             3.44                                                                              --  55.18                                                                              3.63                                                                               --                                       35   131.0-133.5                                                                          C.sub.16 H.sub.11 Cl.sub.2 FN.sub.2 O.sub.3                                             52.06                                                                             3.00                                                                              --  52.61                                                                              3.09                                                                               --                                       36   123-126                                                                              C.sub.17 H.sub.15 ClN.sub.2 O.sub.3                                                     61.73                                                                             4.57                                                                              --  61.63                                                                              4.56                                                                               --                                       37   145-147                                                                              C.sub.16 H.sub.12 ClFN.sub.2 O.sub.3                                                    57.41                                                                             3.61                                                                              --  57.24                                                                              3.73                                                                               --                                       38   119.0-121.0                                                                          C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                       69.66                                                                             5.85                                                                              --  70.12                                                                              5.98                                                                               --                                       39   115.0-117.5                                                                          C.sub.17 H.sub.14 FClN.sub.2 O.sub.3                                                    58.55                                                                             4.05                                                                              --  58.93                                                                              4.16                                                                               --                                       40   117-119                                                                              C.sub.16 H.sub.13 ClN.sub.2 O.sub.2 S                                                   57.74                                                                             3.94                                                                              8.42                                                                               57.80                                                                              3.86                                                                               8.47                                     41   --    C.sub.18 H.sub.18 N.sub.2 O.sub.3                                                       69.66                                                                             5.85                                                                              --  69.65                                                                              6.12                                                                               --                                       42   104-106                                                                              C.sub.16 H.sub.14 N.sub.2 O.sub.2 S                                                     64.40                                                                             4.73                                                                              9.39                                                                               64.48                                                                              4.95                                                                               9.03                                     43   139-142                                                                              C.sub.16 H.sub.13 N.sub.3 O.sub.4 S                                                     55.97                                                                             3.82                                                                              12.24                                                                              55.85                                                                              3.83                                                                               12.18                                    44   152-154                                                                              C.sub.17 H.sub.16 N.sub.2 O.sub.3 S                                                     62.17                                                                             4.91                                                                              8.53                                                                               61.50                                                                              4.78                                                                               8.52                                     45   137-138                                                                              C.sub.16 H.sub.12 Cl.sub.2 N.sub.2 O.sub.3                                              54.72                                                                             3.45                                                                              7.98                                                                               54.72                                                                              3.53                                                                               8.04                                     46   200-205                                                                              C.sub.17 H.sub.15 Cl.sub.2 N.sub.3 O.sub.2                                              56.05                                                                             4.15                                                                              11.54                                                                              55.95                                                                              4.17                                                                               11.29                                    47   86-89 C.sub.19 H.sub.18 Cl.sub.2 N.sub.2 O.sub.3                                              58.02                                                                             4.61                                                                              7.12                                                                               58.16                                                                              4.76                                                                               7.32                                     48   --    C.sub.16 H.sub.12 Cl.sub.2 N.sub.2 O.sub.3                                              54.72                                                                             3.45                                                                              7.98                                                                               54.73                                                                              3.49                                                                               7.72                                     49   96-98 C.sub.17 H.sub.14 Cl.sub.2 N.sub.2 O.sub.3                                              55.90                                                                             3.86                                                                              7.67                                                                               57.13                                                                              4.30                                                                               9.28                                     50   182-183                                                                              C.sub.16 H.sub.12 Cl.sub.2 N.sub. 2 O.sub.3                                             54.72                                                                             3.45                                                                              7.98                                                                               54.50                                                                              3.31                                                                               7.94                                     51   oil   C.sub.17 H.sub.14 Cl.sub.2 N.sub.2 O.sub.3                                              55.90                                                                             3.86                                                                              7.67                                                                               53.58                                                                              3.95                                                                               7.44                                     52   193-195                                                                              C.sub.16 H.sub.15 N.sub.3 OS                                                            64.62                                                                             5.08                                                                              14.13                                                                              64.37                                                                              5.28                                                                               14.07                                    53   238-240                                                                              C.sub.21 H.sub.17 N.sub.3 OS                                                            70.17                                                                             4.77                                                                              11.69                                                                              69.14                                                                              4.86                                                                               11.44                                    54   128.0-131.5                                                                          C.sub.16 H.sub.16 ClFN.sub.2 O.sub.3                                                    56.73                                                                             4.76                                                                              --  56.85                                                                              4.98                                                                               --                                       55   149.5-151.0                                                                          C.sub.13 H.sub.14 FN.sub.3 O.sub.2                                                      59.31                                                                             5.36                                                                              --  59.34                                                                              5.31                                                                               --                                       56   167.5-168.5                                                                          C.sub.13 H.sub.13 ClFN.sub.3 O.sub.2                                                    52.45                                                                             4.40                                                                              --  51.90                                                                              4.37                                                                               --                                       __________________________________________________________________________

The effectiveness of compounds representative of this invention as terrestrial herbicides were evaluated as preemergence herbicides and postemergence herbicides. The test plants were crabgrass, mustard, nightshade, teaweed, velvetleaf, foxtail, quackgrass and morningglory. For the preemergence test, seeds of the type of plants as shown in Table V were sown in fresh soil. In the preemergence test, the soil was sprayed with a solution of the test compound immediately after the seeds were planted. The solution was about a 1% by weight solution of the test compound in phytobland acetone or acetone/water mixtures. The compounds were applied at the rate of 8 lbs active ingredient/acre of soil surface.

Approximately three weeks after spray applications, the herbicidal activity of the compound was determined by visual observation of the treated areas in comparison with untreated controls. These observations are reported in Table V on a scale of 0 to 100% control of plant growth.

In the postemergence test, the soil and developing plants were sprayed about two weeks after the seeds were sown. The compounds were applied at the rate of 8 lbs active ingredient/acre from about a 1% by weight solution of the test compound in acetone. The postemergence herbicidal activity was measured in the same way as the preemergence activity at three weeks following treatment.

The results of both the preemergence and postemergence tests are set forth in Table V below:

                                      TABLE V                                      __________________________________________________________________________     BIOLOGICAL ACTIVITY OF HERBICIDAL CARBINOL CARBAMATES,                         UREAS, AND N-ALPHA SUBSTITUTED ACETYLCARBAMATES                                   Crab      Velvet       Night    Quack                                       Ex.                                                                               grass                                                                             Morningglory                                                                          leaf                                                                               Foxtail                                                                            Mustard                                                                             shade                                                                              Teaweed                                                                             grass                                       __________________________________________________________________________     Pre-emergent Herbicidal Activity                                                1 100                                                                               100    100 100 100  --  100  100                                          2 100                                                                               100    100 100 100  100 100  100                                          3 93 100    100 92  100  100 100  100                                          4 0  0      0   0   0    0   0    0                                            5 0  0      99  12  100  100 100  100                                          6 0  0      12  0   0    0   0    0                                            7 46 52     100 86  100  72  100  30                                           8 0  100    42  72  100  0   65   55                                           9 0  0      98  0   0    0   74   0                                           10 91 98     100 99  100  100 100  26                                          11 0  12     78  6   100  0   54   20                                          12 100                                                                               100    100 97  100  100 100  100                                         13 6  32     100 12  100  100 46   35                                          14 65 100    100 71  100  72  100  30                                          15 0  12     6   0   0    0   12   0                                           16 42 54     100 65  100  100 100  10                                          17 42 100    100 62  100  100 100  20                                          18 30 100    100 82  100  46  0    10                                          19 12 0      100 30  71   0   6    100                                         20 100                                                                               0      100 100 100  100 26   72                                          21 0  0      0   0   0    0   0    0                                           22 84 100    100 54  100  100 100  75                                          23 6  30     100 12  100  12  12   100                                         24 62 100    100 88  100  100 100  100                                         25 100                                                                               100    100 100 100  --  100  100                                         26 100                                                                               65     100 100 100  --  100  100                                         27 100                                                                               62     86  35  100  0   0    100                                         28 -- 0      100 65  100  56  0    100                                         29 100                                                                               100    100 100 100  98  100  30                                          30 0  0      0   0   0    0   6    0                                           31 0  0      6   0   12   0   6    0                                           32 6  0      12  6   88   0   0    0                                           33 0  0      0   0   12   0   0    0                                           34 6  0      6   0   100  6   12   0                                           35 12 0      98  12  56   0   56   10                                          36 0  0      65  0   100  0   100  0                                           37 0  0      0   0   70   0   0    0                                           38 0  0      35  0   65   12  0    0                                           39 12 6      100 42  86   12  30   0                                           40 0  90     56  0   100  0   0    100                                         41 96 100    100 100 100  100 100  40                                          42 -- 0      0   0   0    0   --   0                                           43 42 0      0   0   56   0   --   0                                           44 -- 0      26  0   12   0   --   --                                          45 0  0      0   0   0    0   --   0                                           46 0  0      0   0   0    0   --   --                                          47 0  0      0   0   0    0   --   --                                          48 72 0      0   0   54   --  --   --                                          49 6  0      0   0   0    0   --   0                                           50 20 0      100 0   0    0   94   0                                           51 74 20     0   12  100  6   0    0                                           52 -- 0      0   0   30   0   --   --                                          53 -- 0      0   65  0    0   --   --                                           54*                                                                              20 45     86  20  100  30  72   60                                          55 0  0      30  0   6    0   33   0                                           56 0  0      75  0   100  54  55   0                                           Post-emergent Herbicidal Activity                                               1 6  20     65  0   22   100 20   0                                            2 0  0      26  0   0    32  22   0                                            3 0  0      32  0   0    6   0    0                                            4 0  0      0   0   0    10  10   0                                            5 0  10     78  0   0    100 59   0                                            6 0  0      0   0   72   0   6    0                                            7 0  0      0   0   2    2   0    0                                            8 0  0      10  0   0    32  38   0                                            9 0  6      59  0   0    26  20   0                                           10 0  22     58  0   33   88  38   10                                          11 0  10     0   0   10   54  10   0                                           12 0  35     100 0   32   78  10   0                                           13 0  10     40  0   45   45  20   0                                           14 0  35     38  0   54   80  50   0                                           15 0  --     35  0   32   30  53   0                                           16 0  0      54  0   26   54  72   0                                           17 0  --     50  0   44   80  78   0                                           18 0  42     30  0   40   100 45   20                                          19 0  0      0   0   74   12  0    0                                           20 32 0      73  0   100  100 20   20                                          21 0  0      12  0   20   12  20   0                                           22 0  0      38  35  45   100 44   10                                          23 12 0      38  0   40   100 55   0                                           24 6  19     100 6   100  100 97   10                                          25 76 26     88  22  100  --  94   10                                          26 80 6      88  87  88   100 87   40                                          27 0  --     20  0   20   --  26   0                                           28 -- 26     100 94  100  100 --   20                                          29 0  33     93  6   50   100 46   0                                           30 0  0      0   0   0    0   0    0                                           31 0  0      6   0   0    0   12   0                                           32 0  0      12  0   100  0   50   0                                           33 0  0      20  0   0    0   10   0                                           34 0  0      0   0   0    0   0    0                                           35 0  0      14  0   12   40  6    0                                           36 0  6      12  0   32   26  26   0                                           37 0  0      0   0   32   10  0    0                                           38 0  0      26  0   45   72  30   0                                           39 0  0      45  0   14   32  33   0                                           40 0  0      54  0   95   56  100  0                                           41 100                                                                               100    95  100 100  100 100  0                                           42 0  72     0   0   56   20  --   0                                           43 -- 0      0   0   0    0   --   --                                          44 -- 0      10  0   0    0   --   --                                          45 0  0      10  0   12   0   --   0                                           46 0  30     0   0   12   0   --   --                                          47 0  0      0   0   12   0   --   --                                          48 0  0      6   0   72   0   --   --                                          49 0  0      20  0   6    6   --   0                                           50 0  6      20  0   30   56  42   0                                           51 0  12     --  74  74   90  74   0                                           52 -- 0      0   0   0    0   --   --                                          53 -- 0      0   0   0    0   --   --                                           54*                                                                              6  12     55  0   12   40  59   30                                          55 0  0      0   0   0    0   0    0                                           56 0  0      0   11  0    0   0    0                                           __________________________________________________________________________      *Tested at 4 lbs/acre                                                    

It will be understood that the plant species employed in the above tests are merely representative of a wide variety of plants that can be controlled by the use of the compounds of this invention. The compounds contemplated in this invention may be applied as postemergent and preemergent herbicides according to methods known to those skilled in the art. Compositions containing the compounds as the active ingredient will usually comprise a carrier and/or diluent, either liquid or solid.

Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents. Liquid concentrates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with the aid of suitable surface active emulsifying and dispersing agent.

The choice of dispersing and emulsifying agents and the amount employed is dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the compound. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the compound in the spray so that rain does not re-emulsify the compound after it is applied to the plant and wash it off the plant. Nonionic, anionic, amphoteric or cationic dispersing and emulsifying agents may be employed; for example, the condensation products of alkylene oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, quaternary ammonium compounds, and the like.

Activity can often be enhanced by use of an emulsifiable crop oil such as Surfel, a trademark of the Union Carbide Corporation for a proprietary composition which comprises a phytobland mixture of surfactant and oil. The surfactant is a blend of polyoxyethylene ethers and the oil is a paraffinic petroleum distillate.

In preparation of wettable powder or dust or granulated compositions, the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like. In the formulation of the wettable powders the aforementioned dispersing agents as well as lignosulfonates can be included.

The required amount of the compound contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concentrate will usually vary from about 10 to 95 percent by weight and in the solid formulations from about 0.5 to about 90 percent by weight. Satisfactory sprays, dusts, or granules for general use contain from about 1/4 to 15 pounds of active ingredient per acre.

The herbicides contemplated herein have a high margin of safety in that when used in sufficient amount to control broadleaf weeds they do not burn or injure the crop and they resist weathering which includes wash-off caused by rain, decomposition by ultra-violet light, oxidation, or hydrolysis in the presence of moisture or, at least such decomposition, oxidation, and hydrolysis as would materially decrease the desired characteristic of the compound or impart undesirable characteristic for instance, phytotoxicity, to the compound. It will be appreciated that the compounds of this invention can also be used in combination with other biologically active compounds.

Although the invention has been illustrated by the foregoing examples, it is not to be construed as being limited to the materials employed therein; but rather, the invention encompasses the generic area as hereinafter disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof. 

What is claimed is:
 1. A compound of the formula: ##STR36## wherein: ##STR37## X is O, or NR; Y is O, or S;Z is O, or NR; R is H or alkyl; R¹ through R⁹ inclusive and R¹³ through R¹⁶ inclusive are individually: hydrogen, halogen, alkyl, cycloalkyl, haloalkyl, halocycloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, nitro, cyano: or phenyl, phenoxy, or phenylthio unsubstituted or substituted with alkyl, alkoxy, alkylthio, halogen, nitro, cyano, amino, haloalkyl, alkylamino, dialkylamino, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkanoyl, aroyl, alkenyl, or alkynyl; R¹⁰ is hydrogen, alkyl, cycloalkyl, haloalkyl, halocycloalkyl, aryl, cyano, alkynyl; and R¹¹ and R¹² are individually hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio: or phenoxy; unsubstituted or substituted with halo, alkyl, alkoxy, nitro, cyano, alkylthio, alkylamino; alpha-haloacetyl, acety, alpha-alkylthioacetyl, alpha-aminoacetyl, alpha-alkoxyacetyl, alpha-phosphonoacetyl, phosphinoacetyl, phosphinylacetyl, or propionyl.
 2. A compound according to claim 1 wherein A is ##STR38##
 3. A compound according to claim 1 wherein A is ##STR39##
 4. A compound of the formula: ##STR40## wherein: X is O, or NR;Y is O, or S; Z is O, or NR; R is H or alkyl; R¹ through R⁹ inclusive are individually: hydrogen, halogen, alkyl, cycloalkyl, haloalkyl, halocycloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, nitro, cyano: or phenyl, phenoxy, or phenylthio unsubstituted or substituted with alkyl, alkoxy, alkylthio, halogen, nitro, cyano, amino, haloalkyl, alkylamino, dialkylamino, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkanoyl, aroyl, alkenyl, or alkynyl; R¹⁰ is hydrogen, alkyl, cycloalkyl, haloalkyl, halocycloalkyl, aryl, cyano, alkynyl; and R¹¹ and R¹² are individually hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio: or phenoxy; unsubstituted or substituted with halo, alkyl, alkoxy, nitro, cyano, alkylthio, alkylamino; alpha-haloacetyl, acetyl, alpha-alkylthioacetyl, alpha-aminoacetyl, alpha-alkoxyacetyl, alpha-phosphonoacetyl, phosphinoacetyl, phosphinylacetyl, or propionyl.
 5. A compound according to claim 4 wherein:R¹, R², R³ and R⁴ are hydrogen; and X, Y and Z are O.
 6. A compound according to claim 5 wherein R⁷ and R¹⁰ is hydrogen; and R⁵, R⁶, R⁸, and R⁹ are individually hydrogen, C₁ -C₃ alkyl halogen or haloalkyl.
 7. A compound according to claim 6 wherein:R¹¹ and R¹² are individually hydrogen, C₁ -C₃ alkyl, unsubstituted acetyl or halosubstituted acetyl.
 8. A herbicidal composition comprising an acceptable carrier and a herbicidally effective amount of the compound of claim
 1. 9. A herbicidal composition comprising an acceptable carrier and a herbicidally effective amount of the compound of claim
 2. 10. A herbicidal composition comprising an acceptable carrier and a herbicidally effective amount of the compound of claim
 3. 11. A herbicidal composition comprising an acceptable carrier and a herbicidally effective amount of the compound of claim
 4. 12. A herbicidal composition comprising an acceptable carrier and a herbicidally effective amount of the compound of claim
 5. 13. A herbicidal composition comprising an acceptable carrier and a herbicidally effective amount of the compound of claim
 6. 14. A herbicidal composition comprising an acceptable carrier and a herbicidally effective amount of the compound of claim
 7. 15. A method for the selective control of undesirable vegetation which comprises applying to the locus to be treated a herbicidally effective amount of the composition of claim
 8. 16. A method for the selective control of undesirable vegetation which comprises applying to the locus to be treated a herbicidally effective amount of the composition of claim
 9. 17. A method for the selective control of undesirable vegetation which comprises applying to the locus to be treated a herbicidaly effective amount of the composition of claim
 10. 18. A method for the selective control of undesirable vegetation which comprises applying to the locus to be treated a herbicidally effective amount of the composition of claim
 11. 19. A method for the selective control of undesirable vegetation which comprises applying to the locus to be treated a herbicidally effective amount of the composition of claim
 12. 20. A method for the selective control of undesirable vegetation which comprises applying to the locus to be treated a herbicidally effective amount of the composition of claim
 13. 21. A method for the selective control of undesirable vegetation which comprises applying to the locus to be treated a herbicidally effective amount of the composition of claim
 14. 22. A compound according to claim 7, wherein: R¹¹ and R¹² are individually C₁ -C₃ alkyl, with a maximum combined number of carbon atoms in R¹¹ plus R¹² of 3, unsubstituted acetyl or halo-substituted acetyl.
 23. A compound according to claim 2, wherein R¹ R², R³, R⁴, R¹³, R¹⁴, R¹⁵ R¹⁶ are hydrogen. 